Techniques for the stabilization and assessment of treated copper-, chromium-, and arsenic-contaminated soil

Remediation mainly based on excavation and burial of the contaminated soil is impractical with regard to the large numbers of sites identified as being in need of remediation. Therefore, alternative methods are needed for brownfield remediation. This study was conducted to assess a chemical stabilization procedure of CCA-contaminated soil using iron (Fe)-containing blaster sand (BS) or oxygen-scarfing granulate (OSG). The stabilization technique was assessed with regard to the feasibility of mixing ameliorants at an industrial scale and the efficiency of the stabilization under different redox conditions. The stability was investigated under natural conditions in 1-m3 lysimeters in a field experiment, and the effect of redox conditions was assessed in a laboratory experiment (10 L). The treatments with high additions of ameliorant (8% and 17%) were more successful in both the laboratory and field experiments, even though there was enough Fe on a stochiometric basis even at the lowest addition rates (0.1% and 1%). The particle size of the Fe and the mixing influenced the stabilization efficiency. The development of anaerobic conditions, simulated by water saturation, increases the fraction of arsenic (AsIII) and, consequently, As mobility. The use of high concentrations of OSG under aerobic conditions increased the concentrations of nickel (Ni) and copper (Cu) in the pore water. However, under anaerobic conditions, it decreased the As leaching compared with the untreated soil, and Ni and Cu leaching was not critical. The final destination of the treated soil should govern the amendment choice, that is, an OSG concentration of approximately 10% may be suitable if the soil is to be landfilled under anaerobic conditions. Alternatively, the soil mixed with 1% BS could be kept under aerobic conditions in a landfill cover or in situ at a brownfield site. In addition, the treatment with BS appeared to produce better effects in the long term than treatment with OSG.     

International trade in meat: the tip of the pork chop

This paper provides an original account of global land, water, and nitrogen use in support of industrialized livestock production and trade, with emphasis on two of the fastest-growing sectors, pork and poultry. Our analysis focuses on trade in feed and animal products, using a new model that calculates the amount of "virtual" nitrogen, water, and land used in production but not embedded in the product. We show how key meat-importing countries, such as Japan, benefit from "virtual" trade in land, water, and nitrogen, and how key meat-exporting countries, such as Brazil, provide these resources without accounting for their true environmental cost. Results show that Japan's pig and chicken meat imports embody the virtual equivalent of 50% of Japan's total arable land, and half of Japan's virtual nitrogen total is lost in the US. Trade links with China are responsible for 15% of the virtual nitrogen left behind in Brazil due to feed and meat exports, and 20% of Brazil's area is used to grow soybean exports. The complexity of trade in meat, feed, water, and nitrogen is illustrated by the dual roles of the US and The Netherlands as both importers and exporters of meat. Mitigation of environmental damage from industrialized livestock production and trade depends on a combination of direct-pricing strategies, regulatory approaches, and use of best management practices. Our analysis indicates that increased water- and nitrogen-use efficiency and land conservation resulting from these measures could significantly reduce resource costs.     

Survey of heavy metal pollution and assessment of agricultural soil in Yangzhong district, Jiangsu Province, China

We investigated concentrations of Hg, Cd, Pb, Zn, Cu, As, Ni, and Cr in samples of soil, cereal, and vegetables from Yangzhong district, China. Compared to subsoils, the sampled topsoils are enriched in Hg, Cd, Cu, Pb, Zn, and As. High levels of Cd and Hg are observed in most agricultural soils. Concentrations of Cr and Ni show little spatial variation, and high Cu, Pb, and Zn contents correspond well to areas of urban development. High As contents are primarily recorded at the two ends of the sampled alluvion. The contents of Cd, Hg, and total organic carbon (TOC) increase gradually to maximum values in the upper parts of soil profiles, while Cr and Ni occur in low concentrations within sampled profiles. As, Pb, Cu, and Zn show patterns of slight enrichment within the surface layer. Compared to data obtained in 1990, Cd and Hg show increased concentrations in 2005; this is attributed to the long-term use of agrochemicals. Cr and Ni contents remained steady over this interval because they are derived from the weathering of parent material and subsequent pedogenesis. The measured As, Cu, Pb, and Zn contents show slight increases over time due to atmospheric deposition of material sourced from urban anthropogenic activity. Low concentrations of heavy metals are recorded in vegetables and cereals because the subalkaline environment of the soil limits their mobility. Although the heavy metal concentrations measured in this study do not pose a serious health risk, they do affect the quality of agricultural products.     

Integrated biomonitoring of air quality with plants and lichens: a case study on ambient ozone from central Italy

A biennial integrated survey, based on the use of vascular plants for the bioindication of the effects of tropospheric ozone together with the use of automatic analysers of ozone, as well as the mapping of lichen biodiversity was performed in the area of Castelfiorentino (Tuscany, central Italy). Photochemically produced ozone proved to be a fundamental presence during the warm season, with maximum hourly means reaching 114 ppb, exceeding the information threshold as fixed by EU: the use of supersensitive tobacco Bel-W3 confirmed the opportunity of carrying out detailed cost-effective monitoring surveys. The potential for didactical and educational implications of this methodology are appealing. Critical levels set up for the protection of vegetation have exceeded considerably. The comparison of biomass productivity in sensitive and resistant individuals (NC-S and NC-R white clover clones, in the framework of an European network) provided evidence that ambient ozone levels are associated with relevant reduction (up to 30%) in the performance of sensitive material; effects on flowering were also pronounced. The economic assessment of such an impact deserves attention. Mapping of epiphytic lichen biodiversity – which has been used to monitor air quality worldwide – was not related to ozone geographical distribution as depicted by tobacco response.     

Effects of sewage sludge blending on the coal combustion: a thermogravimetric assessment

Combustion of urban sewage sludge together with coal in existing infrastructures may be a sustainable management option energetically interesting for these materials, usually considered wastes. Thermogravimetric analysis was used to study the combustion of a semianthracite coal and the modifications undergone when adding a small percentage (2%, 5%, 10%) of sewage sludge. Both Differential Scanning Calorimetric analysis and Differential Thermogravimetry burning profiles showed differences between coal and sewage sludge combustion. However, the effects of adding a percentage of sewage sludge equal or smaller than 10% was hardly noticeable in terms of heat release and weight loss during the coal combustion. This was further proved by non-isothermal kinetic analysis, which was used to evaluate the Arrhenius activation energy corresponding to the co-combustion of the blends. This work shows that thermogravimetric analysis may be used as an easy rapid tool to asses the co-combustion of sewage sludge together with coal.     

A comparison of two techniques for studying sediment desorption kinetics of hydrophobic pollutants

A comparison of two techniques (gaseous purge and vial desorption) for studying the kinetics of desorption of hydrophobic pollutants from natural sediments was conducted using identical, pre-equilibrated pollutant-sediment suspensions. Desorption profiles for the two techniques [for Lindane, Aldrin, 2,2'-dichlorobiphenyl (2,2'-DCB), 4,4'-dichlorobiphenyl (4,4'-DCB), and 2,2',6,6'-tetrachlorobiphenyl (TCB)] were then compared, based on the distribution of pollutant mass between the labile (fast) and non-labile (slow) desorption phases and the release rate constants for each phase of release. The vial desorption technique shows many practical advantages over the gaseous purge technique, including its more realistic mixing conditions, the use of an independent sample for each data point (as opposed to a calculation of a cumulative mass purged at each time point), the fact that the vials constitute a closed system and are therefore less subject to ambient contamination, and the relatively low demands of time and money for the vial technique. No consistent trends in labile rate constants or in pollutant distribution between the labile and non-labile phase were observed between the two techniques. A comparison of kinetic parameters shows much faster non-labile rate constants for the gaseous purge technique, attributed to the violent, continuous agitation employed, which likely disrupted sediment aggregates and oxidized the natural organic matter associated with the sediment. Non-labile rate constants have implications for the long-term fate of compounds adsorbed to repetitively disturbed sediments. This study suggests that the traditionally less popular vial desorption technique may yield more realistic non-labile desorption rate constants.     

Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

Oxidation of trichloroethene over metal oxide catalysts: kinetic studies and correlation with adsorption properties

The performance of bulk chromium oxide is compared with that of a Mn commercial catalyst for the deep oxidation of trichloroethene (1000-2500ppmv, 55h(-1) space velocity) in air, in dry and wet (20000ppm of H(2)O) conditions, in terms of activity, selectivity and stability. Chromium oxide was found to be more active (on a catalyst weight basis), however its activity decreases continuously with time on stream. The presence of water increases its stability, the Mn catalyst showing the opposite behaviour. The effect of water on the Cr catalyst can be explained according to the Deacon equilibrium, as the presence of water tends to decrease the Cl(2) concentration, assumed to be responsible of the catalyst deactivation. Regarding to the selectivity, the Mn catalyst yields C(2)Cl(4), CCl(4) and CHCl(3) as organochlorinated by-products, whereas chromium oxide produces only trace amounts of CCl(4). Simple power-law kinetics expressions (first-order for Mn and zero-order for Cr) provide fairly good fits for the evolution of the conversion with the temperature. Furthermore, the kinetic behaviour of chromium oxide can be represented with a Langmuir-Hinshelwood model taking into account the chlorine inhibitory effect.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

A field trial for an ex-situ bioremediation of a drilling mud-polluted site

The remediation of drilling mud-polluted sites in the Southeast of Mexico is a top priority for Mexican oil industry. The objective of this work was to find a technology to remediate these sites. A field trial was performed by composting in biopiles, where four 1ton soil-biopiles were established, one treatment in triplicate and one unamended biopile. Amended biopiles were added with nutrients to get a C/N/P ratio of 100/3/0.5 plus a bulking agent (straw) at a soil/straw ratio of 97/3. Moisture content was maintained around 30-35%. Results showed that, after 180 d, total petroleum hydrocarbon (TPH) concentrations decreased from 99300+/-23000mgTPHkg(-1) soil to 5500+/-770mgTPHkg(-1) for amended biopiles and to 22900+/-7800mgTPHkg(-1) for unamended biopile. An undisturbed soil control showed no change in TPH concentrations. Gas chromatographic analysis showed residual alkyl dibenzothiophene type compounds. Highest bacterial counts were observed during the first 30 d which correlated with highest TPH removal, whereas fungal count increased at the end of the experimentation period. Results suggested an important role of the straw, nutrient addition and water content in stimulating aerobic microbial activity and thus hydrocarbon removal. This finding opens an opportunity to remediate old polluted sites with recalcitrant and high TPH concentration.